CN101277991B - Resin composition for stereo planography - Google Patents
Resin composition for stereo planography Download PDFInfo
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- CN101277991B CN101277991B CN2006800363719A CN200680036371A CN101277991B CN 101277991 B CN101277991 B CN 101277991B CN 2006800363719 A CN2006800363719 A CN 2006800363719A CN 200680036371 A CN200680036371 A CN 200680036371A CN 101277991 B CN101277991 B CN 101277991B
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- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
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- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
- C08F290/14—Polymers provided for in subclass C08G
- C08F290/144—Polymers containing more than one epoxy group per molecule
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/24—Di-epoxy compounds carbocyclic
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
- C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
- C08G65/16—Cyclic ethers having four or more ring atoms
- C08G65/18—Oxetanes
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- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0037—Production of three-dimensional images
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- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
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Abstract
The invention provides a resin composition for stereolithography, which is low in absorption of water and moisture even when the composition is preserved for a long time, which is capable of maintaining high curing sensitivity for long, which is capable of fabricating a three-dimensional object in a shortened molding time, smoothly and in high productivity, the three-dimensional object being excellent in molding accuracy, dimensional accuracy, water resistance, moisture resistance, and mechanical characteristics. A resin composition for stereolithography (i) includes: an epoxy compound (A); an ethylenic unsaturated compound (B); a photo initiator for cationic polymerization (C); a photo initiator for radical polymerization (D); and an oxetane compound (E), (ii) an epoxy compound containing an alicyclic diglycidyl ether compound is included as the epoxy compound (A) in a proportion of 20 to 100 weight% with respect to a total weight of the epoxy compound (A), the alicyclic diglycidyl ether compound being represented by formula (I): in which R<1> represents a hydrogenated bisphenol A residue, a hydrogenated bisphenol F residue, a hydrogenated bisphenol Z residue, a cyclohexanedimethanol residue, or a tricyclodecanedimethanol residue, and (iii) an oxetane compound containing: a monooxetane compound (E1) having one oxetane group in a molecule thereof; and a polyoxetane compound (E2) having two or more oxetane groups in a molecule thereof is included as the oxetane compound (E) in a weight ratio of the monooxetane compound (E1) to the polyoxetane compound (E2) of 95:5 to 5:95.
Description
Technical field
The present invention relates to a kind of resin combination that is used for optical three-dimensional molded object, even if when it stores under its uncured state for a long time, absorptivity to water and moisture is also low, it can keep the high susceptibility (actinic radiation susceptibility) of solidifying for a long time, and it can be by the irradiation of actinic radiation, successfully and with high productivity optics prepare three-dimensional body in the preparation time that shortens, this three-dimensional body has outstanding preparation accuracy, size accuracy, water tolerance, wet fastness and mechanical property.
Background technology
In recent years, the optical three-dimensional molded object of resin combination that is input as the liquid light curing on basis with data in the three-dimensional CAD is able to extensive employing, and reason is to need not to prepare the three-dimensional body of just can the preparation size accuracy good expection of metallic mold.
A kind of illustrative method as optical three-dimensional molded object, can be for the example of following method: the Ultra-Violet Laser selectivity irradiation that computerizeds control be placed on the fluid surface of the liquid light curing resin composition in the container, thereby solidifies the specific thickness that has required pattern; Then for one deck liquid resin composition is provided on this cured layer, and with this resin combination of Ultra-Violet Laser irradiation, similar to the above with its curing; Repeat cumulative operation and obtain continuous cured layer, finally to obtain three-dimensional body.This optical three-dimensional molded object makes easily and the preparation object that obtains having suitable complicated shape in short period relatively becomes possibility.
For resin that is used for optical three-dimensional molded object or resin combination, need various features.For example, need be to the degree of cure susceptibility of actinic radiation, the preparation medium viscosity is low and operational capability outstanding, aging back is low to the absorptivity of water and moisture and the reduction of solidifying susceptibility less, the high resolving power of the object of preparation and outstanding preparation accuracy, solidify in volumetric shrinkage little and by solidifying outstanding mechanical features, water tolerance, wet fastness and the thermotolerance of object of preparation.
As the resin combination that is used for optical three-dimensional molded object, photo curable acrylate resin composition, photo curable polyurethane acrylate resin composition, photo curable composition epoxy resin, photo curable Epocryl composition and photo curable vinyl ether resin composition have been proposed and have used.In these photo curable resin combinations, photo curable composition epoxy resin owing to can form the preparation object of size accuracy excellence, is attracting people's attention in recent years.
Yet, it may be noted that the positively charged ion that produces by the photo curable composition epoxy resin of irradiation reacts, and make speed of response slow, and preparation needs for a long time.Therefore, in order to improve speed of response, proposed to add low-molecular-weight polyol compound, for example ethylene glycol or propylene glycol to photo curable composition epoxy resin.In addition, in order to shorten preparation time by improving speed of response, a kind of resin combination (with reference to patent document 1) that is used for optical three-dimensional molded object has been proposed, it is a kind of photo curable resin combination, comprise the organic compound (for example epoxy compounds) of cationically polymerizable and the organic compound of free redical polymerization, and further comprise the polyester polyols alkylol cpd.Yet in both cases, the size accuracy of resulting preparation article is low, still has the problem of water tolerance and wet fastness.
In addition, proposed to add oxetane compound, shortened preparation time (referring to patent document 2 and 3) to improve photocuring susceptibility and to be designed at the resin combination that is used for optical three-dimensional molded object that comprises the organic compound of cationically polymerizable (for example epoxy compounds).
Add the resin combination that is used for optical three-dimensional molded object of oxetane compound and improved photocuring susceptibility really owing to added oxetane compound.Yet, according to studying in great detail of the inventor, have been found that: comprise the specific absorption height of the resin combination that is used for optical three-dimensional molded object of oxetane compound water and moisture; When said composition is preserved under the high humidity state, greatly reduce its photocuring susceptibility owing to absorbing water and moisture at short notice in a large number, thereby worsened processability; The degradation of resulting preparation object, and lost the effect of adding oxetane compound.
Patent document 1:JP-B-103218
Patent document 2:JP-A-10-168165
Patent document 3:JP-A-2004-217934
Summary of the invention
The technical problem that solves
An object of the present invention is to provide a kind of resin combination that is used for optical three-dimensional molded object, it is to the curing susceptibility height of actinic radiation, it can higher yields prepare object in short actinic radiation irradiation time, and its specific absorption to water and moisture is low further, even and if preserve the reduction that also can not follow curing performance under the high humidity state, and it can keep the high susceptibility of solidifying for a long time.
Another object of the present invention provides a kind of resin combination that is used for optical three-dimensional molded object, its preparation accuracy is outstanding, and it can prepare except above-mentioned and goes out the color characteristic size accuracy under high humidity and the outstanding three-dimensional body of mechanical features, water tolerance, wet fastness and thermotolerance.
The method of dealing with problems
In order to address the above problem, the inventor has repeated conscientious research.The inventor finds as a result, comprising epoxy compounds, ethylenically unsaturated compounds, the light trigger that is used for cationoid polymerisation, be used for the light trigger of radical polymerization initiator and the resin combination that is used for optical three-dimensional molded object of oxetane compound, when the compound that mainly comprises specific alicyclic 2-glycidyl ether compound is used as epoxy compounds, and further when the single oxetane compound that in molecule, has an oxetane groups and the polyoxy heterocycle butane compound that in molecule, has two or more oxetane groups with specified weight than as oxetane compound the time, can obtain being used for the resin combination of optical three-dimensional molded object, it is to the curing susceptibility height of actinic radiation, it can be with the produced in high yields three-dimensional body in short preparation time, its specific absorption to moisture and moisture is low, even and if composition preserves the reduction that also can not follow curing performance under the high humidity state, and it can keep the high susceptibility of solidifying for a long time.
The inventor further finds, it is outstanding that the above-mentioned resin combination that is used for optical three-dimensional molded object that obtains prepares accuracy, has multiple outstanding feature with this each three-dimensional body of resin combination system that is used for optical three-dimensional molded object, for example size accuracy, mechanical features, water tolerance, wet fastness and the thermotolerance under high humidity.
The inventor also finds, by using specific compound as above-mentioned various single oxetane compound and the polyoxy heterocycle butane compound that is used for the resin combination of optical three-dimensional molded object, can further improve above-mentioned various feature, and on the basis of this understanding, finish the present invention.
That is, the present invention is as follows.
(1) a kind of resin combination that is used for optical three-dimensional molded object (i) comprises:
Epoxy compounds (A);
Ethylenically unsaturated compounds (B);
The light trigger (C) that is used for cationoid polymerisation;
The light trigger (D) that is used for radical polymerization; With
Oxetane compound (E),
(ii) comprising the epoxy compounds that contains alicyclic 2-glycidyl ether compound as epoxy compounds (A), gross weight with respect to epoxy compounds (A), ratio is 20～100 weight %, and this alicyclic 2-glycidyl ether compound is by shown in the formula (I):
R wherein
1Expression Hydrogenated Bisphenol A residue, A Hydrogenated Bisphenol A F residue, A Hydrogenated Bisphenol A Z residue, cyclohexanedimethanol residue or tristane dimethanol residue and
(iii) the oxetane compound that wherein comprises as oxetane compound (E) contains: the single oxetane compound (E1) that has an oxetane groups in its molecule; With the polyoxy heterocycle butane compound (E2) that has two or more oxetane groups at its molecule; Single oxetane compound (E1) is 95: 5～5: 95 with the weight ratio of polyoxy heterocycle butane compound (E2).
And the present invention is as follows.
(2) as the resin combination that is used for optical three-dimensional molded object of above-mentioned (1), wherein polyoxy heterocycle butane compound (E2) is by the polyoxy heterocycle butane compound shown in the formula (II):
Two R wherein
2Identical or different, expression has the alkyl of 1～5 carbon atom respectively; R
3Expression has or does not have the divalent organic group of aromatic nucleus; M represents 0 or 1.
(3) as the resin combination that is used for optical three-dimensional molded object of above-mentioned (1) or (2), wherein single oxetane compound (E1) is by the single oxetane compound shown in the formula (III):
R wherein
4Expression has the alkyl of 1～5 carbon atom.
(4) as each the resin combination that is used for optical three-dimensional molded object in above-mentioned (1)～(3), wherein with respect to the epoxy compounds (A) of 100 weight parts, the ratio of the oxetane compound that comprises (E) is 5～60 weight parts.
The invention effect
The curing susceptibility height that is used for the resin combination of optical three-dimensional molded object to actinic radiation of the present invention can be with the required three-dimensional body of produced in high yields in short preparation time.
The resin combination that is used for optical three-dimensional molded object of the present invention is low to the specific absorption of water and moisture, even and composition is preserved for some time and still can not be followed the reduction of curing performance under the high humidity state, it can keep outstanding curing susceptibility for a long time, even if it is after prolonged preservation, even if still can prepare the three-dimensional body that still has outstanding various physical propertiess (comprising mechanical features) after long-time the preservation smoothly.
It is outstanding that the resin combination that the present invention is used for optical three-dimensional molded object prepares accuracy, has outstanding feature with the three-dimensional body that is used for the resin combination preparation of optical three-dimensional molded object of the present invention, for example size accuracy, mechanical features, water tolerance, wet fastness, thermotolerance etc.Preferred implementation
Describe the present invention below in detail.
Being used in the presence of the light trigger of cationoid polymerisation, when with photochemical radiation, Resins, epoxy of the present invention (A) produces polyreaction and/or crosslinking reaction.
" actinic radiation " in this specification sheets is meant the energy-ray that can solidify the resin combination that is used for optical three-dimensional molded object, for example ultraviolet rays, electron beam, X ray, radiation and high frequency waves.
In the present invention, as Resins, epoxy (A), the epoxy compounds that uses comprises by the alicyclic 2-glycidyl ether compound shown in the following formula (I) (below be called " alicyclic 2-glycidyl ether compound (I) "), based on the gross weight of epoxy compounds (A), ratio is 20～100 weight %:
In formula (I), R
1Expression Hydrogenated Bisphenol A residue, A Hydrogenated Bisphenol A F residue, A Hydrogenated Bisphenol A Z residue, cyclohexanedimethanol residue or tristane dimethanol residue.
In the present invention, by the ratio of using alicyclic 2-glycidyl ether compound (I) content be the epoxy compounds of 20～100 weight % as epoxy compounds (A), further improved the curing properties, resolving power and the transmission of ultraviolet rays that solidify susceptibility, thick-layer.In addition, the viscosity that has reduced this resin combination that is used for optical three-dimensional molded object to be being prepared smoothly, and further reduced the volumetric shrinkage factor of the object that is obtained by optical three-dimensional molded object.
When the content ratio of alicyclic 2-glycidyl ether compound (I) during, under super-humid conditions, reduced the dimensional stability of preparation object less than 20 weight % of epoxy compounds (A) gross weight.
As Resins, epoxy (A), preferably use the ratio of alicyclic 2-glycidyl ether compound (I) content to be 30～100 weight % of epoxy compounds (A) gross weight, the epoxy compounds of preferred especially 50～100 weight %, thereby not only improved the wet fastness of preparation object, and the aging size fluctuation that causes diminishes.
As alicyclic 2-glycidyl ether compound (I) concrete among the present invention, Hydrogenated Bisphenol A diglycidylether, A Hydrogenated Bisphenol A F diglycidylether, A Hydrogenated Bisphenol A Z diglycidylether, cyclohexanedimethanodiglycidyl diglycidyl ether and tristane dimethanol diglycidylether can be the examples.In the present invention, as alicyclic 2-glycidyl ether compound (I), above-mentioned diglycidylether can a kind of independent use, and perhaps two or more can be used in combination.In the alicyclic 2-glycidyl ether compound (I) of above-mentioned example, from the availability and the anti-moisture absorption angle of preparation object, Hydrogenated Bisphenol A diglycidylether and/or tristane dimethanol diglycidylether are preferred uses the among the present invention.
As other epoxy compounds that can be used in combination with alicyclic 2-glycidyl ether compound (I) as the part of epoxy compounds (A), can use any epoxy compounds, as long as it is being used for can carrying out cationoid polymerisation in the presence of the light trigger of cationoid polymerisation, and, for example, the alicyclic epoxide compound except that alicyclic 2-glycidyl ether compound (I), aliphatic epoxy compound and aromatic epoxy compound can be the examples.As other epoxy compoundss, more preferably use the polyepoxy compound that in molecule, has two or more epoxide groups.
As other above-mentioned alicyclic epoxide compounds, for example, having the polyglycidyl ether of polyhydroxy-alcohol of at least one alicyclic ring and the compound that contains epoxy cyclohexane or cyclopentane epoxide by the compound epoxidation that comprises tetrahydrobenzene or cyclopentenes ring is obtained is the example.The more specifically example of other cycloaliphatic epoxy resins comprises, for example, 3,4-epoxycyclohexyl methyl-3 ', 4 '-epoxycyclohexane carboxylate, 2-(3,4-epoxycyclohexyl-5,5-spiral shell-3,4-epoxy group(ing))-hexanaphthene-two
Alkane, two (3,4-epoxycyclohexyl methyl) adipic acid ester, vinyl cyclohexene dioxide, 4-vinyl epoxy-cyclohexane, two (3,4-epoxy-6-methyl cyclohexane ylmethyl) adipic acid ester, 3,4-epoxy-6-methylcyclohexyl-3,4-epoxy-6-methylcyclohexanecarboxylic acid ester, methylene radical two (3, the 4-epoxy cyclohexane), two (3 of dicyclopentadiene diepoxide, ethylene glycol, 4-epoxycyclohexyl methyl) ether, ethylene (3, the 4-epoxycyclohexane carboxylate), epoxy six hydrogen dioctyl phthalates and epoxy six hydrogen phthalandiones two-2-ethylhexyl.
As the aliphatic epoxy compound, for example, many glycidyl esters of the polyglycidyl ether of aliphatics polyhydroxy-alcohol or its oxirane adducts and aliphatic long-chain polyprotonic acid can be the examples.More specifically, for example 1, the diglycidylether of 4-butyleneglycol, 1, the diglycidylether of 6-hexylene glycol, the triglycidyl ether of glycerine, the triglycidyl ether of TriMethylolPropane(TMP), four glycidyl ethers of Sorbitol Powder, six glycidyl ethers of Dipentaerythritol, the diglycidylether of polyoxyethylene glycol, the diglycidylether of polypropylene glycol, by one or both or multiple oxirane and aliphatics polyhydroxy-alcohol (ethylene glycol for example, propylene glycol or glycerine) polyglycidyl ether of the polyether glycol that obtains of addition, with the 2-glycidyl ester of aliphatic long-chain diprotic acid can be the example.Except that above-mentioned epoxy compounds, for example, the glycidyl ester of the monoglycidyl ether of aliphatics higher alcohols, higher fatty acid, epoxidised soybean oil, butyl epoxy stearate, octyl epoxy stearate, epoxy linseed oil and epoxidized polybutadiene can be the examples.
As above-mentioned aromatic epoxy compound, have the monohydroxy of at least one fragrant nucleolus or list or polyglycidyl ether or its oxirane adducts of polyhydroxy phenol.Particularly, for example, the glycidyl ether that obtains by the reaction of dihydroxyphenyl propane or Bisphenol F, or the oxirane adducts of itself and epoxy chloropropane and epoxy phenolics, phenol, cresols, butylphenol or can be the example by the monoglycidyl ether of the Aethoxy Sklerol that its adduction oxirane is obtained.
In the present invention, as the epoxy compounds of non-alicyclic 2-glycidyl ether compound (I), can use one or both or multiple above-mentioned epoxy compounds.In above-mentioned these other epoxy compoundss, from solidifying the reactivity and the mechanical features of object, preferred bisphenol A diglycidyl ether, the bisphenol A diglycidyl ether of oxyethane modification, the bisphenol A diglycidyl ether, 3 of epoxy pronane modification of using, 4-epoxycyclohexyl-3 ', 4 '-epoxycyclohexane carboxylate, trihydroxymethylpropanyltri diglycidyl ether and T 55.
As unsaturated allyl compound (B), can use by being used for to produce any compound of polyreaction and/or crosslinking reaction with photochemical radiation in the presence of the light trigger of radical polymerization.As the exemplary embodiment of this compound, can exemplify (methyl) acrylic compound and unsaturated polyester compound.These ethylenically unsaturated compounds can a kind of independent uses or can be used two or more.
In these compounds, as ethylenically unsaturated compounds (B), preferably use the compound that has at least one (methyl) acrylic acid groups in a molecule, specific examples comprises (methyl) acrylate, polyester (methyl) acrylate and polyethers (methyl) acrylate of epoxy compounds and (methyl) acrylic acid reaction product, alcohol.
As the epoxy compounds that can be used as ethylenically unsaturated compounds (B) and (methyl) acrylic acid reaction product, epoxy (methyl) acrylate reaction product that is obtained by aromatic epoxy compound, alicyclic epoxide compound and/or aliphatic epoxy compound and (methyl) acrylic acid reaction can be the example.In these compounds, preferred epoxy (methyl) the series of acrylate reaction product that obtains by aromatic epoxy compound and the reaction of (methyl) vinylformic acid of using.Specific examples comprises epoxy (methyl) the series of acrylate reaction product that is obtained by glycidyl ether and the reaction of (methyl) vinylformic acid, described glycidyl ether is obtained by bisphenol cpd (for example dihydroxyphenyl propane or Bisphenol F or its oxirane adducts) and epoxidizing agent (for example epoxy chloropropane) reaction, and reacts epoxy (methyl) the series of acrylate reaction product that obtains by epoxy phenolics and (methyl) vinylformic acid.
As (methyl) acrylate of the alcohol that can be used as ethylenically unsaturated compounds (B), can be the example with (methyl) acrylate that the reaction of (methyl) vinylformic acid obtains by the aromatic alcohols that in molecule, has at least one hydroxyl, fatty alcohol, alicyclic alcohol and/or its oxirane adducts.
More specifically, for example, (methyl) 2-EHA, (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 2-hydroxy propyl ester, (methyl) lauryl acrylate, (methyl) stearyl acrylate ester, (methyl) Isooctyl acrylate monomer, (methyl) tetrahydrofurfuryl acrylate, (methyl) isobornyl acrylate, (methyl) benzyl acrylate, two (methyl) vinylformic acid 1, the 4-butanediol ester, two (methyl) vinylformic acid 1,6-hexylene glycol ester, two (methyl) vinylformic acid binaryglycol ester, two (methyl) vinylformic acid triglycol ester, two (methyl) vinylformic acid DOPCP, two (methyl) polyalkylene glycol acrylate ester, two (methyl) vinylformic acid polypropylene glycol ester, three (methyl) vinylformic acid trihydroxymethylpropanyl ester, three (methyl) vinylformic acid pentaerythritol ester, six (methyl) vinylformic acid dipentaerythritol ester, other many (methyl) vinylformic acid dipentaerythritol ester, above-mentioned polyhydroxy-alcohol (glycol for example, triol, tetrol, six alcohol etc.) (methyl) acrylate of oxirane adducts, the bisphenol a diacrylate of oxyethane modification, the bisphenol a diacrylate of epoxy pronane modification etc. can be the example.
In these compounds, (methyl) acrylate as alcohol, by (methyl) acrylate that has two or more (methyl) acrylic acid groups in a molecule that polyvalent alcohol and the reaction of (methyl) vinylformic acid obtain, for example many (methyl) vinylformic acid dipentaerythritol ester is preferred the use.
In addition, in above-mentioned (methyl) acrylic compound, consider polymerization velocity, acrylic compound is preferably methacrylate compound.
In addition, as polyester (methyl) acrylate that can be used as ethylenically unsaturated compounds (B), polyester (methyl) acrylate that is obtained by polyester that comprises hydroxyl and the reaction of (methyl) vinylformic acid can be the example.
In addition, as polyethers (methyl) acrylate, the polyether acrylate that is obtained by polyethers that comprises hydroxyl and vinylformic acid reaction can be the example.
In above-mentioned ethylenically unsaturated compounds, as ethylenically unsaturated compounds (B), consider the reactivity and the mechanical features of cured product, the preferred in the present invention epoxy acrylate (for example " VR-77 " that obtains by bisphenol A diglycidyl ether and vinylformic acid reaction that uses, by Showa Kobunshi Co., the Ltd. preparation), isobornyl acrylate, lauryl acrylate, the different stearyl ester of vinylformic acid, six vinylformic acid dipentaerythritol ester, five vinylformic acid dipentaerythritol ester, the pentaerythritol tetracrylate of oxyethane modification, Viscoat 295 with the oxyethane modification.
In the present invention, as the light trigger that is used for cationoid polymerisation (C) (hereinafter only being called " cationic polymerization initiators (C) " sometimes), any polymerization starter that can pass through to cause the cationoid polymerisation of epoxy compounds (A) with photochemical radiation.In polymerization starter,, preferably use by discharging lewis acidic salt with photochemical radiation as cationic polymerization initiators (C).As the example of salt, belong to the aromatic series sulfonium salt of VIIa family element, the aromatic series salt that belongs to the aromatic series salt of VIa family element and belong to Va elements can be the example.Particularly, hexafluoro-antimonic acid triaryl matte, Tetrafluoroboric acid triphenylbenzene acylphosphanes, hexafluoro-antimonic acid triphenylsulfonium, two [4-(the phenylbenzene sulfonium base) phenyl] sulfide of two two hexafluoro-antimonic acids, two [4-(two-the 4 '-hydroxyl-oxethyl phenyl sulfonium base) phenyl] sulfide of two two hexafluoro-antimonic acids, two [4-(phenylbenzene-sulfonium base) phenyl] sulfide of two two phosphofluoric acids and Tetrafluoroboric acid phenylbenzene iodine can be the examples.
In the present invention, can use in these cationic polymerization initiators one or both or multiple.In cationic polymerization initiators, more preferably use the aromatic series sulfonium salt.
If desired, in order to increase speed of response, can use photosensitizers, for example benzophenone, benzoin alkylether, thioxanthone etc. with cationic polymerization initiators.
As the light trigger that is used for radical polymerization (D) (hereinafter only being called " radical polymerization initiator (D) " sometimes), can use any polymerization starter that can pass through to cause the radical polymerization of ethylenically unsaturated compounds (B) with photochemical radiation.As the example, can exemplify its phenmethyl or dialkyl group acetal compound, benzophenone compound, acetophenone compound, its bitter almond oil camphor or alkylether compounds, benzophenone cpd, thioxanthone compound etc.
Particularly, as its phenmethyl or dialkyl group acetal compound, for example benzyl dimethyl ketal, phenmethyl-'beta '-methoxy ethyl-acetal etc. are the examples.
As the benzophenone compound, for example 1-hydroxyl-cyclohexyl benzophenone can be the example.
As acetophenone compound, for example diethoxy acetophenone, 2-hydroxymethyl-1-phenyl third-1-ketone, 4 '-sec.-propyl-2-hydroxy-2-methyl Propiophenone, 2-hydroxy-2-methyl Propiophenone, right-the dimethylamino benzoylformaldoxime, right-tertiary butyl dichloroacetophenone, right-tertiary butyl Trichloroacetophenon, right-nitrine benzylidene acetophenone etc. can be the examples.
As the bitter almond oil camphor compound, for example bitter almond oil camphor, benzoin methyl ether, bitter almond oil camphor ethyl ether, bitter almond oil camphor isopropyl ether, bitter almond oil camphor n-butyl ether, bitter almond oil camphor isobutyl ether etc. can be the examples.
As benzophenone cpd, benzophenone, neighbour-benzoylbenzoic acid methyl esters, Michaelis (Michler ' s) ketone, 4 for example, 4 '-two diethyl-aminobenzophenones, 4,4 '-dichloro benzophenone etc. can be the examples.
As the thioxanthone compound, for example thioxanthone, 2-methyl thioxanthone, 2-ethyl thioxanthone, 2-clopenthixal ketone, 2-isopropyl thioxanthone etc. can be the examples.
In the present invention, according to required performance, can mix one or both or multiple radical polymerization initiator (D).
As radical polymerization initiator (D), the tone good (yellow chromaticity is little) for resulting cured product preferably uses 1-hydroxyl-cyclohexyl benzophenone in the present invention.
The resin combination that is used for the optical stereo lithography among the present invention comprises oxetane compound (E) together with epoxy compounds (A), ethylenically unsaturated compounds (B), cationic polymerization initiators (C) and radical polymerization initiator (D).
In the present invention, as oxetane compound (E), need to use the polyoxy heterocycle butane compound (E2) that has single oxetane compound (E1) of an oxetane groups and have two or more oxetane groups in molecule in molecule, single oxetane compound (E1): the weight ratio of polyoxy heterocycle butane compound (E2) is 95: 5～5: 95.
Because like this, this resin combination that is used for optical three-dimensional molded object becomes extremely slow to the uptake rate of water and moisture, make be convenient said composition under high wet condition during prolonged preservation, its absorption to water-content or moisture is still low, and can keep its initial height to solidify susceptibility for a long time.
When single oxetane compound (E1) departs from scope of the present invention based on the ratio of oxetane compound (E) weight, and when surpassing 95 weight % (when the ratio of polyoxy heterocycle butane compound (E2) during) less than 5 weight %, this wet fastness that is used for the resin combination of optical three-dimensional molded object reduces, and when the ratio of single oxetane compound (E1) during less than 5 weight % (when the ratio of polyoxy heterocycle butane compound (E2) surpasses 95 weight %), this mechanical features that solidifies object reduces, make the specific absorption step-down of water and moisture under any circumstance, can not obtain the resin combination that is used for optical three-dimensional molded object of can the processing machinery feature outstanding three-dimensional body.
In oxetane compound (E), single oxetane compound (E1): the weight ratio of polyoxy heterocycle butane compound (E2) is preferably 10: 90～and 90: 10, more preferably 20: 80～80: 20.
As single oxetane compound (E1), can use any compound, as long as it has an oxetane groups in a molecule, but preferably use the single trimethylene oxide monohydroxy-alcohol compound that in a molecule, has an oxetane groups and an alcoholic extract hydroxyl group.
In so single trimethylene oxide monohydroxy-alcohol compound, owing to acquisition easily, hyperergy and low viscous reason, more preferably use by the single trimethylene oxide monohydroxy-alcohol compound shown in the following formula (III) (hereinafter being called " single trimethylene oxide alcohol (III) " sometimes) as single oxetane compound (E1).
R wherein
4Expression has the alkyl of 1～5 carbon atom.
In formula (III), as R
4Example, can exemplified by methyl, ethyl, propyl group, butyl and amyl group.
As the specific examples of single trimethylene oxide alcohol (III), 3-hydroxymethyl-3-methyl trimethylene oxide, 3-hydroxymethyl-3-ethyl trimethylene oxide, 3-hydroxymethyl-3-propyl group trimethylene oxide, 3-hydroxyl-methyl-3-normal-butyl trimethylene oxide, 3-hydroxymethyl-3-propyl group trimethylene oxide etc. can be the examples.These compounds can a kind of independent use, perhaps can use two or more.In these compounds, owing to obtain easily and reactivity, 3-hydroxymethyl-3-methyl trimethylene oxide and 3-hydroxymethyl-3-ethyl trimethylene oxide more preferably uses.
As polyoxy heterocycle butane compound (E2), can use any the have compound of two oxetane groups, the compound that has the compound of three oxetane groups and have four oxetane groups, but the preferred compound with two oxetane groups that uses.
Wherein, consider the mechanical features of availability, reactivity, agent of low hygroscopicity and curing object, preferably use by the dioxetanes hydride compounds (II) shown in the following formula (II) (hereinafter being called " dioxetanes hydride compounds (II) " sometimes) as polyoxy heterocycle butane compound (E2).
In formula (II), two R
2Can be identical or different, each expression has the alkyl of 1～5 carbon atom; R
3Expression has or does not have the divalent organic group of aromatic nucleus; M represents 0 or 1.
In formula (II), as R
2Example, can exemplified by methyl, ethyl, propyl group, butyl and amyl group.As R
3Example, can exemplify straight chain with 1～12 carbon atom and branched alkylidene (for example ethylidene, propylidene, butylidene, inferior neo-pentyl, positive pentamethylene, positive hexa-methylene etc.), by formula-CH
2-Ph-CH
2-or-CH
2-Ph-Ph-CH
2-shown in divalent group, Hydrogenated Bisphenol A residue, A Hydrogenated Bisphenol A F residue, A Hydrogenated Bisphenol A Z residue, hexanaphthene-dimethanol residue, tristane dimethanol residue etc.
As the specific examples of dioxetanes hydride compounds (II), by following formula (IIa) or the dioxetanes hydride compounds (IIb) can be the example.
In formula, two R
2Can be identical or different, each expression has the alkyl of 1～5 carbon atom; R
3Expression has or does not have the divalent organic group of aromatic nucleus.
Specific examples by the dioxetanes hydride compounds shown in the formula (IIa) comprises two (3-methyl-3 oxa-cyclobutylmethyl) ethers, two (3-ethyl-3-oxa-cyclobutylmethyl) ether, two (3-propyl group-3-oxa-cyclobutylmethyl) ether, two (3-butyl-3-oxa-cyclobutylmethyl) ether etc.
As specific examples by the dioxetanes hydride compounds shown in the formula (IIb), can exemplify by two R wherein of the dioxetanes hydride compounds shown in the formula (IIb)
2All represent methyl, ethyl, propyl group, butyl or amyl group, R
3Expression ethylidene, propylidene, butylidene, inferior neo-pentyl, positive pentamethylene, positive hexa-methylene etc., by formula-CH
2-Ph-CH
2-or-CH
2-Ph-Ph-CH
2-shown in divalent group, Hydrogenated Bisphenol A residue, A Hydrogenated Bisphenol A F residue, A Hydrogenated Bisphenol A Z residue, cyclohexanedimethanol residue, tristane dimethanol residue.
In these compounds, as polyoxy heterocycle butane compound (E2), since the mechanical features of its easy acquisition, agent of low hygroscopicity and curing object, preferred wherein two R that use
2All represent methyl or ethyl by the dioxetanes hydride compounds shown in the formula (IIa), that is, and two (3-methyl-3-oxa-cyclobutylmethyl) ethers and/or two (3-ethyl-3-oxa-cyclobutylmethyl) ether.Especially, more preferably use two (3-ethyl-3-oxa-cyclobutylmethyl) ethers.
Consider viscosity, speed of response, the preparation speed of composition, the size accuracy and the mechanical features of preparing product, the resin combination that is used for optical three-dimensional molded object of the present invention preferably comprises, based on the resin combination gross weight that is used for optical three-dimensional molded object, ratio is the epoxy compounds (A) of 10～80 weight %, preferred especially 15～75 weight %, with ratio be the ethylenically unsaturated compounds (B) of 2～60 weight %, preferred especially 5～50 weight %.
In addition, the resin combination that is used for optical three-dimensional molded object of the present invention preferably comprises, based on composition total weight, ratio is the cationic polymerization initiators (C) of 0.1～10 weight %, preferred especially 0.5～10 weight %, with ratio be the radical polymerization initiator (D) of 0.1～10 weight %, preferred especially 0.5～10 weight %.
The resin combination preferred package oxygen heterocyclic ring butane compound (E) that is used for optical three-dimensional molded object of the present invention, ratio is every 1D0 weight part epoxy compounds (A) 5～60 weight parts, the ratio that more preferably comprises it is 6～50 weight %, 10～45 weight % more preferably, thus the curing susceptibility of the resin combination that is used for optical three-dimensional molded object increased.
When oxetane compound (E) content after a little while, this curing susceptibility that is used for the resin combination of optical three-dimensional molded object reduces, and preparation needs a large amount of time, and when the content of oxetane compound (E) is too big, the water absorbability that not only is used for the resin combination of optical three-dimensional molded object increases, and the mechanical features and the thermotolerance of curing object also reduce.
If desired, the resin combination that the present invention is used for Seterolithography can comprise one or both or multiple tinting material (for example pigment and dyestuff), defoamer, levelling agent, thickening material, fire retardant, antioxidant, the filler (cross-linked polymer particle, silicon-dioxide, glass powder, ceramic powder, metal-powder etc.) of appropriate amount, with be used for modified resins, only otherwise can influence effect of the present invention gets final product.
In the optical three-dimensional molded object that uses resin combination of the present invention, can use any known stereolithography method and apparatus.As the exemplary stereolithography method that can preferably adopt, following method can be the example: with actinic radiation selectivity irradiation liquid resin composition of the present invention to obtain having the cured layer of required pattern; Uncured liquid resin composition and same with this resin combination of photochemical radiation, to be cured with top identical mode is provided on this cured layer then; Repeat this preparation manipulation forming the cured layer of continuous cured layer, thereby finally obtain required three-dimensional body.
As actinic radiation at that time, as mentioned above, ultraviolet ray, electron beam, X-ray, radiation and high frequency waves can be the examples.In actinic radiation, from economic angle, optimal wavelength is the ultraviolet ray of 300～400nm.As light source at that time, can use ultraviolet laser (for example semi-conductor excites solid laser, Ar laser apparatus, He-Cd laser apparatus etc.), high voltage mercury lamp, ultrahigh pressure mercury lamp, mercury lamp, xenon lamp, halogen lamp, metal halide lamp, ultraviolet LED (photodiode), luminescent lamp etc.
Preparation surface at the resin combination by being used for optical three-dimensional molded object with photochemical radiation forms each curing resin layer with designated shape pattern, can focus on the actinic radiation of any such as the point of laser beam is painted or the line method of painting forms curing resin layer by use.Can adopt actinic radiation to see through wherein to arrange for example regional imaging mask of liquid crystal shutter or digital micro-mirror dimmer (DMD) of a plurality of low-light dimmers, to preparing that regional irradiation is carried out on the surface and the method that forms curing resin layer.
The resin combination that is used for optical three-dimensional molded object of the present invention can be widely used in the optical three-dimensional molded object field, as exemplary example, can exemplify testing vision design the functional model of model, detection part, be used to prepare the resin die of mold, the direct mould that is used to prepare the matrix model of metal pattern and is used for the model metal pattern.Especially, the resin combination that is used for optical three-dimensional molded object of the present invention can effectively prepare the model that is used for precise part.More specifically, the resin combination that is used for optical three-dimensional molded object of the present invention can be effective to process for example model, master mold and the mould of precise part, electricity and electronic unit, furniture, building structure, trolley part, various container and mold.
Embodiment
The present invention specifically describes with reference to embodiment, but the present invention never is defined in this.In an embodiment, unless otherwise noted, " part " is meant " weight part "
In the following embodiments, to the evaluation of the mensuration of the water-content of the resin combination that is used for optical three-dimensional molded object, curing performance, by the mensuration of the mechanical features (flexural strength, flexural modulus of elasticity, tensile strength, tensional modulus of elasticity, tensile elongation, surface hardness) of the object of optical three-dimensional molded object preparation and following the carrying out of test of heat-drawn wire.
(1) is used for the water-content of the resin combination of optical three-dimensional molded object
Use " the capacity titration type water-content determinator; KF-06 type (a capacity titration type watercontent measuring equipment, Model KF-06) " of Mitsubishi Chemical Corporation preparation to measure the water-content of the resin combination that is used for optical three-dimensional molded object according to Karl Fischer method.
(2) be used for the curing performance of the resin combination of optical three-dimensional molded object
By using the Photocurable resin composition that obtains in following examples or the Comparative Examples, carry out the optics preparation according to the method described in following examples and the Comparative Examples (particularly embodiment 1 and Comparative Examples 1).In each resin combination, curing performance with resin combination that enough cured film thickness and its film thickness can measure with the constant voltage slide calliper rule is rated " good ", the curing performance of the resin combination that its film thickness is difficult to measure is rated " slightly poor ", and more weak and its film thickness of cured film can't be rated " bad " with what the constant voltage slide calliper rule were measured.
(3) optics prepares the deflection test of object:
By using the optics in following embodiment 1 or the Comparative Examples 1 to prepare object (shaped specimens that meets JISK-7171), test the flexural strength and the flexural modulus of elasticity of this test specimen according to JIS K-7171.
(4) optics prepares anti-test of object:
By using the optics in following embodiment 1 or the Comparative Examples 1 to prepare object (the dumbbell shaped test specimen that meets JISK-7113), test the tensile strength and the tensional modulus of elasticity of this test specimen according to JIS K-7113.
(5) optics prepares the surface hardness of object
By using the optics in following embodiment 1 or the Comparative Examples 1 to prepare object (the dumbbell shaped test specimen that meets JISK-7113), according to JIS K-7253, by the sclerometer method, the surface hardness that " Asker type D sclerometer (the Asker type D hardness meter) " for preparing with KobunshiKeiki Co. tests this test specimen.
(6) optics prepares the heat-drawn wire of object
Optical mode goods by using in following embodiment 1 or the Comparative Examples 1 preparation (shaped specimens that adapts with JISK-7171), by applying the 1.813MPa load to the test specimen that meets JIS K-7207 (A), use Toyo Seiki Seisaku-Sho, Ltd. Zhi Bei " HDT Tester6M-2 ", the heat-drawn wire of testing this test specimen.
Embodiment 1
(1) passes through 2 part 3,4-epoxycyclohexyl methyl-3 ', 4 '-epoxycyclohexane carboxylate, 58 parts of Hydrogenated Bisphenol A diglycidylethers, 5 parts of 3-hydroxymethyl-3-ethyl trimethylene oxide, 15 parts of two (3-ethyl-3-oxa-cyclobutylmethyl) ethers, 4 parts of hexafluoro-antimonic acid triaryl mattes are as cationic polymerization initiators (" UVI-6974; by The Dow Chemical Company preparation "), vinylformic acid dipentaerythritol ester more than 10 parts (" NK Ester A-9530 ", by Shin NakamuraChemical Co., Ltd. prepare) and 3 parts of 1-hydroxycyclohexylphenylketones (" Iragacure 184 ", by Ciba Specialty Chemicals Inc. preparation) (radical initiator) mix fully, prepares photo curable resin combination.
(2) (i) be 1020ppm, as shown in following table 1 according to the water-content of the photo curable resin combination that obtains in the aforesaid method test above-mentioned (1).
In addition, the photo curable resin combination that obtains in above-mentioned (1) being stored in moisture control is in 60% the moisture eliminator.Take out this photo curable resin combination of fixed amount after wearing out from container, test water content simultaneously, (ii) carries out the optics preparation with the photo curable resin combination that takes out according to following method.The curing performance of this photo curable resin combination when preparing according to aforesaid method evaluation optics simultaneously, is measured or is estimated the optics that obtains by above method and prepare the absorbent properties of object and the curability of this resin.Measure the result of following various character according to aforesaid method.
(ii) optics preparation
By using ultra-high speed optics formation system (" SOLIFORM500B ", by Teijin SeikiCo., Ltd. prepare) and " semi-conductor excites solid laser BL6 type (semiconductorexcitation solid state laser BL6 type) " (output: 1000mW, wavelength: 355nm, by Spectra Physics preparation), at 80mJ/cm
2The condition of section pitch (cumulative thickness) of irradiation energy, 0.10mm under, irradiation is carried out on surface perpendicular to the photo curable resin combination that obtains in above-mentioned (i), carry out the optics preparation, meet the dumbbell shaped test specimen of JIS K-7113 and meet the shaped specimens of JIS K-7171 with preparation, and test its physical properties according to aforesaid method.What obtain the results are shown in the following table 1.
Comparative Examples 1
(1) passes through 2 part 3,4-epoxycyclohexyl methyl-3 ', 4 '-the epoxy-cyclohexane carboxylicesters, 58 parts of Hydrogenated Bisphenol A diglycidylethers, 20 parts of 3-hydroxymethyl-3-ethyl trimethylene oxide, 4 parts of hexafluoro-antimonic acid triaryl mattes are as cationic polymerization initiators (" UVI-6974 ", by TheDow Chemical Company preparation), vinylformic acid dipentaerythritol ester more than 10 parts (" NK EsterA-9530 ", by Shin Nakamura Chemical Co., Ltd. prepare) and 3 parts of 1-hydroxycyclohexylphenylketones (" Iragacure 184 ", by Ciba Specialty Chemicals Inc. preparation) (radical initiator) mix fully, prepares photo curable resin combination.
(2) water-content according to the photo curable resin combination that obtains in the aforesaid method mensuration above-mentioned (1) is 980ppm, as shown in following table 1.
In addition, the photo curable resin combination that obtains in above-mentioned (1) is stored in moisture control in 60% moisture eliminator.Take out this photo curable resin combination of fixed amount after aging from container, test its water-content, simultaneously, with the photo curable resin combination of taking-up according to embodiment 1 in the (ii) identical method of method of (2), carry out the optical 3-dimensional moulding.The curing performance of this photo curable resin combination when estimating the optical 3-dimensional moulding according to aforesaid method, and by above method test or estimate the absorbent properties of the optics molded object that obtains and the curability of this resin.What obtain the results are shown in the following table 1.
As the result in the table 1 as seen, the water-absorbent of the photo curable resin combination among the embodiment 1 (resin combination that is used for optical three-dimensional molded object) is low, even if after it is placed, still can keep curing performance for a long time well, make in addition after 20 days by carrying out optics with photoirradiation when preparing, still can obtain good tensile strength and mechanical features.
On the contrary, the water-content of the photo curable resin combination in the Comparative Examples 1 (resin combination that is used for the optical 3-dimensional moulding) after 4 days just up to about 8000ppm, make the uptake rate height of this resin combination to water, and curing performance will reduce in early days, in addition, the mechanical features of resulting three-dimensional shaped bodies is also low.
Embodiment 2
(1) passes through 20 part 3,4-epoxycyclohexyl methyl-3 ', 4 '-epoxycyclohexane carboxylate, 40 parts of Hydrogenated Bisphenol A diglycidylethers, 10 parts of 3-hydroxymethyl-3-ethyl trimethylene oxide, 10 parts of two (3-ethyl-3-oxa-cyclobutylmethyl) ethers, 4 parts of hexafluoro-antimonic acid triaryl mattes are as cationic polymerization initiators (" UVI-6974 ", by The Dow Chemical Company preparation), vinylformic acid dipentaerythritol ester more than 10 parts (" NK Ester A-9530 ", by ShinNakamura Chemical Co., Ltd. prepare) and 3 parts of 1-hydroxycyclohexylphenylketones (" Iragacure 184 ", by Ciba Specialty Chemicals Inc. preparation) (radical initiator) mix fully, prepares photo curable resin combination.
(2) water-content according to the photo curable resin combination that obtains in the aforesaid method mensuration above-mentioned (1) is 780ppm.
In addition, the photo curable resin combination that obtains in above-mentioned (1) being stored in moisture control is in 60% the moisture eliminator 14 days.After the storage, take out this photo curable resin combination of fixed amount from container, the water-content of mensuration is 7500ppm.With store after 14 days photo curable resin combination according to embodiment 1 in the (ii) identical method of (2) carry out the optics preparation.The curing performance of this photo curable resin combination when preparing according to aforesaid method evaluation optics.This curing performance is good.
Comparative Examples 2
(1) passes through 20 part 3,4-epoxycyclohexyl methyl-3 ', 4 '-epoxycyclohexane carboxylate, 40 parts of Hydrogenated Bisphenol A diglycidylethers, 20 parts of 3-hydroxymethyl-3-ethyl trimethylene oxide, 4 parts of hexafluoro-antimonic acid triaryl mattes are as cationic polymerization initiators (" UVI-6974 ", by TheDow Chemical Company preparation), vinylformic acid dipentaerythritol ester more than 10 parts (" NK EsterA-9530 ", by Shin Nakamura Chemical Co., Ltd. prepare) and 3 parts of 1-hydroxycyclohexylphenylketones (" Iragacure 184 ", by Ciba Specialty Chemicals Inc. preparation) (radical initiator) mix fully, prepares photo curable resin combination.
(2) water-content according to the photo curable resin combination that obtains in the aforesaid method mensuration above-mentioned (1) is 820ppm.In addition, the photo curable resin combination that obtains in above-mentioned (1) being stored in moisture control is in 60% the moisture eliminator 14 days.After the storage, take out this photo curable resin combination of fixed amount from container, measure its water-content up to 13500ppm.With store after 14 days photo curable resin combination according to embodiment 1 in the (ii) identical method of (2) carry out the optics preparation.The curing performance of this photo curable resin combination when preparing according to aforesaid method evaluation optics.Curing performance is low, only can obtain weak solidified film.
Embodiment 3～6
(1) passes through 2 part 3,4-epoxycyclohexyl methyl-3 ', 4 '-the epoxy-cyclohexane carboxylicesters, alicyclic 2-glycidyl ether compound shown in 58 parts of following tables 2,5 parts of 3-hydroxymethyl-3-ethyl trimethylene oxide, 15 parts of two (3-ethyl-3-oxa-cyclobutylmethyl) ethers, 3 parts of hexafluoro-antimonic acid triaryl mattes are as cationic polymerization initiators (" UVI-6974 ", by The DowChemical Company preparation), vinylformic acid dipentaerythritol ester more than 15 parts (" NK EsterA-9530 ", by Shin Nakamura Chemical Co., Ltd. prepare) and 3 parts of 1-hydroxycyclohexylphenylketones (" Iragacure 184 ", by Ciba Specialty Chemicals Inc. preparation) (radical initiator) mix fully, prepares various photo curable resin combinations.
(2) the various photo curable resin combination that obtains in above-mentioned (1) being stored in moisture control is in 60% the moisture eliminator 14 days.After the storage, take out this photo curable resin combination of fixed amount from container, measure its water-content.The measurement result of various resin combinations is shown in the following table 2.With store after 14 days photo curable resin combination according to embodiment 1 in the (ii) identical method of (2) carry out the optics preparation.The curing performance of various photo curable resin combinations when preparing according to aforesaid method evaluation optics.As shown in following table 2, the curing performance of every kind of resin combination is all good.
Embodiment 7～12
(1) passes through 10 part 3,4-epoxy group(ing) cyclohexyl methyl-3 ', 4 '-the epoxy-cyclohexane carboxylicesters, 50 parts of Hydrogenated Bisphenol A diglycidylethers, 5 parts of 3-hydroxymethyl-3-ethyl trimethylene oxide, dioxetanes hydride compounds shown in 15 parts of tables 3,3 parts of hexafluoro-antimonic acid triaryl mattes are as cationic polymerization initiators (" UVI-6974 ", by The Dow Chemical Company preparation), vinylformic acid dipentaerythritol ester more than 15 parts (" NK Ester A-9530 ", by ShinNakamura Chemical Co., Ltd. prepare) and 3 parts of 1-hydroxycyclohexylphenylketones (" Iragacure 184 ", by Ciba Specialty Chemicals Inc. preparation) (radical initiator) mix fully, prepares various photo curable resin combinations.
(2) the various photo curable resin combination that obtains in above-mentioned (1) being stored in moisture control is in 60% the moisture eliminator 14 days.After the storage, take out this photo curable resin combination of fixed amount from container, measure water-content.The measurement result of various resin combinations is shown in the following table 3.With store after 14 days photo curable resin combination according to embodiment 1 in the (ii) identical method of (2) carry out the optics preparation.The curing performance of this photo curable resin combination when preparing according to aforesaid method evaluation optics.As shown in following table 3, the curing performance of every kind of resin combination is all good.
Used dioxetanes hydride compounds (IIc among the embodiment 7～12
1)～(IIc
6) be by the dioxetanes hydride compounds shown in the following formula (IIc):
(IIc
1) be a kind of dioxetanes hydride compounds, wherein R
3Represent new pentylidene;
(IIc
2) be a kind of dioxetanes hydride compounds, wherein R
3Represent positive pentamethylene;
(IIc
3) be a kind of dioxetanes hydride compounds, wherein R
3Represent positive hexa-methylene;
(IIc
4) be a kind of dioxetanes hydride compounds, wherein R
3Expression 1, the 4-xylylene;
(IIc
5) be a kind of dioxetanes hydride compounds, wherein R
3Representative ring hexane-1, the 4-dimethylene;
(IIc
6) be a kind of dioxetanes hydride compounds, wherein R
3Expression A Hydrogenated Bisphenol A-4,4 '-dimethylene.
Industrial applicibility
The resin combination that is used for optical three-dimensional molded object of the present invention is that convenient said composition is under its uncured state during long-time the storage, absorptivity to water and moisture is also low, it can keep the high susceptibility (to the susceptibility of actinic radiation) of solidifying for a long time, and when when preparing with photochemical radiation, its can be in short molding time smoothly and high productivity flash of light preceding an earthquake length of schooling is equipped with three-dimensional body, this three-dimensional body has outstanding preparation accuracy, size accuracy, water tolerance, wet fastness and mechanical property.Therefore, use the resin combination that is used for optical three-dimensional molded object of the present invention, can prepare speed, high size accuracy and successfully obtain being used for the model or the mould of processing precise parts, Electrical and Electronic assembly, furniture, building structure, trolley part, various container, mold, metal pattern and master mold with height; Be used to design complicated thermal medium loop parts, be used to analyze and plan the parts of the behavior of thermal medium with complex construction; With other various three dimensional molded objects with complicated shape and structure.
Claims (3)
1. resin combination that is used for optical three-dimensional molded object (i) comprises:
Epoxy compounds (A);
Ethylenically unsaturated compounds (B);
The light trigger (C) that is used for cationoid polymerisation;
The light trigger (D) that is used for radical polymerization; With
Oxetane compound (E),
(ii) comprising the epoxy compounds that contains alicyclic 2-glycidyl ether compound as epoxy compounds (A), ratio is 20～100 weight % of epoxy compounds (A) gross weight, this alicyclic 2-glycidyl ether compound is represented by formula (I):
R wherein
1Expression Hydrogenated Bisphenol A residue, A Hydrogenated Bisphenol A F residue, A Hydrogenated Bisphenol A Z residue, cyclohexanedimethanol residue or tristane dimethanol residue and
(iii) wherein as oxetane compound (E), the oxetane compound that comprises contains: the single oxetane compound (E1) that has an oxetane groups in its molecule, with the polyoxy heterocycle butane compound (E2) that has two or more oxetane groups in its molecule, single oxetane compound (E1) is 95: 5～5: 95 with the weight ratio of polyoxy heterocycle butane compound (E2);
Wherein said single oxetane compound (E1) is by the single oxetane compound shown in the formula (III):
R wherein
4Expression has the alkyl of 1～5 carbon atom.
2. the resin combination that is used for optical three-dimensional molded object according to claim 1, wherein said polyoxy heterocycle butane compound (E2) are by the polyoxy heterocycle butane compound shown in the formula (II):
Two R wherein
2Identical or different, each expression has the alkyl of 1～5 carbon atom; R
3The divalent organic group m that expression has or do not have aromatic nucleus represents 0 or 1.
3. the resin combination that is used for optical three-dimensional molded object according to claim 1, wherein with respect to the epoxy compounds (A) of 100 weight parts, the ratio of included oxetane compound (E) is 5～60 weight parts.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP283644/2005 | 2005-09-29 | ||
| JP2005283644 | 2005-09-29 | ||
| PCT/JP2006/319582 WO2007037434A1 (en) | 2005-09-29 | 2006-09-29 | Resin composition for optical three-dimensional molded object |
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| Publication Number | Publication Date |
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| CN101277991A CN101277991A (en) | 2008-10-01 |
| CN101277991B true CN101277991B (en) | 2011-11-09 |
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| CN2006800363719A Active CN101277991B (en) | 2005-09-29 | 2006-09-29 | Resin composition for stereo planography |
Country Status (6)
| Country | Link |
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| US (1) | US20100152314A1 (en) |
| EP (1) | EP1939234B2 (en) |
| JP (1) | JP5478016B2 (en) |
| KR (1) | KR101341081B1 (en) |
| CN (1) | CN101277991B (en) |
| WO (1) | WO2007037434A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP5305580B2 (en) * | 2005-11-04 | 2013-10-02 | 富士フイルム株式会社 | Oxetane compounds |
| JP5280615B2 (en) | 2006-06-16 | 2013-09-04 | シーメット株式会社 | Optical three-dimensional resin composition |
| TWI464193B (en) * | 2007-03-15 | 2014-12-11 | Nippon Steel & Sumikin Chem Co | Oxetane resin composition, optical materials and optical semiconductor packaging materials |
| KR101433413B1 (en) * | 2007-03-20 | 2014-08-26 | 디에스엠 아이피 어셋츠 비.브이. | Stereolithography resin compositions and three-dimensional objects made therefrom |
| JP5119846B2 (en) * | 2007-04-18 | 2013-01-16 | 住友ベークライト株式会社 | Epoxy resin composition and transparent composite sheet |
| WO2009001420A1 (en) * | 2007-06-25 | 2008-12-31 | Cmet Inc. | Optical three-dimensional molding polymerizable resin composition |
| WO2010104603A2 (en) * | 2009-03-13 | 2010-09-16 | Dsm Ip Assets B.V | Radiation curable resin composition and rapid three-dimensional imaging process using the same |
| JP5301409B2 (en) * | 2009-10-05 | 2013-09-25 | 株式会社日本触媒 | Cationic curable resin composition and cured product thereof |
| EP2842980B1 (en) * | 2013-08-09 | 2021-05-05 | DSM IP Assets B.V. | Low-viscosity liquid radiation curable dental aligner mold resin compositions for additive manufacturing |
| EP3971235A1 (en) | 2013-11-05 | 2022-03-23 | Covestro (Netherlands) B.V. | Stabilized matrix-filled liquid radiation curable resin compositions for additive fabrication |
| US20180046076A1 (en) * | 2015-03-23 | 2018-02-15 | Dow Global Technologies Llc | Photocurable Compositions for Three-Dimensional Printing |
| EP3347399B1 (en) | 2015-09-09 | 2020-12-09 | Carbon, Inc. | Epoxy dual cure resins for additive manufacturing |
| JP7008398B2 (en) * | 2016-03-31 | 2022-01-25 | 株式会社Adeka | Curable composition, method for producing cured product, and cured product thereof |
| EP3597669A1 (en) | 2018-07-20 | 2020-01-22 | Clariant International Ltd | Photo-curable resin composition for 3d printing |
| EP3597668A1 (en) | 2018-07-20 | 2020-01-22 | Clariant International Ltd | Photo-curable resin composition for 3d printing |
| CN111363101A (en) * | 2020-03-30 | 2020-07-03 | 上海信斯帝克新材料有限公司 | Light-cured resin composition and method for 3D printing by using same |
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| US5981616A (en) * | 1996-12-13 | 1999-11-09 | Dsm N.V. | Photo-curable resin composition used for photo fabication of three-dimensional objects |
| CN1354763A (en) * | 1999-04-19 | 2002-06-19 | Dsm有限公司 | Resin composition for photofabrication of three dimensional objects |
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| JPH07103218B2 (en) | 1988-09-13 | 1995-11-08 | 旭電化工業株式会社 | Resin composition for optical modeling |
| US6287745B1 (en) * | 1998-02-18 | 2001-09-11 | Dsm N.V. | Photocurable liquid resin composition comprising an epoxy-branched alicyclic compound |
| JP2002060463A (en) * | 2000-08-17 | 2002-02-26 | Jsr Corp | Photocurable resin composition and three-dimensionally shaped article |
| JP3876630B2 (en) * | 2001-03-01 | 2007-02-07 | 東亞合成株式会社 | Curable composition |
| AU2003224516A1 (en) * | 2002-05-03 | 2003-11-17 | Dsm Ip Assets B.V. | Radiation curable resin composition and rapid prototyping process using the same |
| US20040054025A1 (en) * | 2002-06-20 | 2004-03-18 | Lawton John A. | Compositions comprising a benzophenone photoinitiator |
| KR100729898B1 (en) * | 2002-10-11 | 2007-06-18 | 도아고세이가부시키가이샤 | Cationically polymerizable composition containing metal oxide particles |
| US20040137368A1 (en) | 2003-01-13 | 2004-07-15 | 3D Systems, Inc. | Stereolithographic resins containing selected oxetane compounds |
| DE112004001151B4 (en) † | 2003-06-24 | 2021-06-02 | Cmet Inc. | Three-dimensional object and method for its manufacture |
| US8338074B2 (en) † | 2003-06-25 | 2012-12-25 | Cmet Inc. | Actinic radiation-curable stereolithographic resin composition having improved stability |
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2006
- 2006-09-29 WO PCT/JP2006/319582 patent/WO2007037434A1/en active Application Filing
- 2006-09-29 KR KR1020087007429A patent/KR101341081B1/en active IP Right Grant
- 2006-09-29 EP EP06798487.2A patent/EP1939234B2/en active Active
- 2006-09-29 CN CN2006800363719A patent/CN101277991B/en active Active
- 2006-09-29 US US12/088,522 patent/US20100152314A1/en not_active Abandoned
- 2006-09-29 JP JP2007537743A patent/JP5478016B2/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5981616A (en) * | 1996-12-13 | 1999-11-09 | Dsm N.V. | Photo-curable resin composition used for photo fabication of three-dimensional objects |
| CN1354763A (en) * | 1999-04-19 | 2002-06-19 | Dsm有限公司 | Resin composition for photofabrication of three dimensional objects |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1939234A1 (en) | 2008-07-02 |
| JP5478016B2 (en) | 2014-04-23 |
| EP1939234B2 (en) | 2018-04-11 |
| KR101341081B1 (en) | 2013-12-12 |
| KR20080053315A (en) | 2008-06-12 |
| WO2007037434A1 (en) | 2007-04-05 |
| JPWO2007037434A1 (en) | 2009-04-16 |
| EP1939234A4 (en) | 2010-07-28 |
| CN101277991A (en) | 2008-10-01 |
| EP1939234B1 (en) | 2011-11-09 |
| US20100152314A1 (en) | 2010-06-17 |
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